Mono or bis 3-(polypropyl or butyl-propenyl)-amino alkyl piperazines

ABSTRACT

Title compounds are novel oil-soluble, detergent-dispersant addition products for crankcase lubricating oils and are prepared by reacting a primary or secondary amine with 1-chloro-2-methylpropenyl substituted alkane hydrocarbons, especially 1-chloro-2-methylpropenyl terminated butene polymers, having a total of 20 to 180 carbon atoms.

RELATED APPLICATIONS

This is a division of application Ser. No. 391,590 filed Aug. 27, 1973,which is a continuation in part of application Ser. No. 116,722 filedFeb. 11, 1971, now abandoned.

BACKGROUND OF THE INVENTION

N-hydrocarbyl amines can be prepared by known methods through thereaction of a hydrocarbon monochloride and a nitrogen-containingcompound having at least one hydrogen atom on a nitrogen atom. Theproblem encountered in that preparative route is the obtension of areactive hydrocarbon monochloride when the desired N-hydrocarbylsubstituent is to be derived from a mono-alkene hydrocarbon having aterminal double bond. Direct chlorination of such an alkene hydrocarbonwith liquid or gaseous chlorine results in random chain chlorination,chlorination of side chains and the formation of products containing therelatively unreactive neopentyl chloride. Such a product is relativelyunreactive with HN< containing compounds. Chlorination of ethyleniccompounds with peroxidecatalyzed sulfuryl chloride (SO₂ Cl₂) isdescribed by M. S. Kharasch and H. C. Brown in J.A.C.S. 61, 3432-34. Forexample there is described such chlorination of cyclohexene todichlorocyclohexane, allyl chloride to 1,2,3-trichloro propane, sym.dichloroethylene to sym. tetrachloroethane, stilbene to d,d' andβ,β'-stilbene dichlorides and tetrapenylethylene to its dichloride. Ineach instance that chlorination of ethylenic compound added chlorines toboth sides of the double bond and produce a saturated compound. Theauthors in that and prior articles point out that such sulfuryl chloridereaction of ethylenic compounds not peroxide-catalyzed is either so slowas to be not feasible for even laboratory use or does not proceed atall.

Chlorination with liquid or gaseous chlorine of alkenes having aterminal double bond or an internal double bond can be readily conductedto high chlorine contents. For example, a polybutene of averagemolecular weight of about 2000 can be so chlorinated to a 35% chlorinecontent. But the resulting chlorinated alkene is relatively unreactivewith such HN< group nitrogen-containing compounds or even alkali metalhydroxides because most of the chlorine atom substituents are ratherstably bound.

N-hydrocarbyl derivatives of aliphatic polyamines havinghydrocarbyl-substituents of from about 700 to about 100,000 in molecularweight (50-7145 carbon atoms) are described in U.S. Pat. No. 3,275,554as non-ash forming detergent addition agents for mineral lubricant oils.

SUMMARY OF INVENTION

It has now been found that N-hydrocarbyl substituted amines having lowermolecular weight hydrocarbyl substituents, e.g. from about 350 up toabout 2500 in molecular weight (about 25 to about 180 carbon atoms) areuseful detergent addition agents for lighter hydrocarbon fractions suchas gasoline, kerosene, diesel fuel and heating oils. Of these, theN-hydrocarbyl-substituted amines whose hydrocarbyl-substituents areslightly branched, such as those derived from Friedel-Crafts catalyzed(AlCl₃) polymerization of propene or butenes, respectively, to liquidviscous polypropylenes or polybutylenes are more advantageously usefulfor that detergent purpose. Also found are that N-hydrocarbylsubstituted bis(amino-alkyl) piperazine, alkylene polyamines anddi(hydroxyalkyl) polyalkylene polyamines whose hydrocarbyl-substituentshave an average molecular weight of 700-2500 are excellent motorcrankcase oil detergents.

SPECIFIC EMBODIMENTS

The necessary reactant for preparation of such useful N-hydrocarbylsubstituted amines are the 1-chloropropenyl terminated alkanes,especially propene and butene polymers, which have, in general, a singleterminal unsaturated group as in the formula ##EQU1## wherein R' ishydrogen or methyl and R comprises repeating propyl or butyl groups insuch numbers to provide with the indicated terminal unsatured 3-propenylor 2-methylpropenyl group a total of about 25 to 180 number averagecarbon atoms. The preparation of such 1-chloropropenyl terminated alkanehydrocarbons is taught in the above-mentioned copending applicationwhose disclosure is incorporated herein by reference.

In general, the 1-chloropropenyl or 1-chloro-2-methylpropenylsubstituted alkane hydrocarbon can be prepared by first reacting at atemperature of 175°F, in the absence of peroxide catalyst but in thepresence of benzene as solvent, 1.0-1.5 moles of sulfuryl chloride (SO₂Cl₂) per mole of the propenyl terminated alkane to produce, as indicatedin equation I below, the indicated 1,2-dichloropropyl terminated alkaneand by-product SO₂ and then dehydrochlorinating such 1,2-dichloropropylterminated alkane, as indicated in equation II below, to the indicated1-chloropropenyl terminated alkane and by-product HCl. ##EQU2## In bothequations R and R' are the same as before defined.

Dehydrochlorination of the indicated 1,2-dichloropropyl or1,2-dichloro-2-methylpropyl terminated alkane can be accomplished withanhydrous sodium or potassium carbonate or hydroxide; alkaline earthmetal oxide, hydroxide or carbonates; or other chemical compound usefulfor dehydrochlorination which leaves no non-volatile acidic residue, andpreferably leaves a chloride-containing residue which is insoluble inbenzene or the 1-chloropropenyl terminated alkene. Dehydrochlorinationof the indicated 1,2-dichloropropenyl or 1,2-dichloro-2-methylpropenylterminated alkane also can be accomplished thermally at a temperature of300°-400°F. While such termally splitting out of HCl leaves some of itin the resulting reaction mass, such remaining HCl conveniently isremoved by distilling off benzene. Advantageously, reactions I and IIcan be conducted sequentially without prior removal of by-product SO₂.Reaction I is conducted with reflux of benzene solvent and part ofby-product SO₂ is driven off while heating the first reaction mass tothe termperature of 300°-400°F, part of by-product HCl is driven off asit is formed at such temperature and any residual amounts of SO₂ and thelast amount of HCl to be split out can be removed while distilling offbenzene. The removal of SO₂ and splitting out of HCl as well as itsremoval conveniently can be accomplished by injecting an inert gas (e.g.nitrogen or carbon dioxide) into the reaction mass while heating thefirst reaction mass to a temperature of 300°-400°F. and continuing inertgas injection until benzene solvent has been removed and HCl is nolonger present in the exhaust gas.

Any of the before illustrated propenyl terminated alkanes having a totalof 20-180 carbon atoms (M.W. of 280-2520) are useful as startinghydrocarbon reactant for preparation of the foregoing 1-chloropropenylor 1-chloro-2-methylpropenyl terminated alkane. For example, suchpropenyl terminated alkane can be a product of cracking petroleum or afraction thereof or a double bond isomerized fraction or compound sofirst produced. An excellent source of such propenyl or 2-methylpropenylterminated alkane, as before indicated, are the commercially available280-2520 number average molecular weight liquid viscous polypropenes orpolybutenes derived from the Friedel-Crafts catalyzed polymerization ofpropene or butenes. Such polybutenes are commercially produced by saidpolymerization of isobutylene, mixtures containing isobutylene andbutene-1and/or butene-2 and even such mixtures, a petroleum refiningfraction of C₄ hydrocarbons known as B-B stream, which in addition tosuch butenes also contain butane and a small amount, 1-5%, butadiene.

The present inventive N-hydrocarbyl amines are, as before indicated,derived by reacting a bis(aminoalkyl) piperazine, alkylene polyamine orN-di(hydroxyalkyl) polyalkylene polyamine with the aforementioned1-chloropropenyl or 1-chloro-2-methylpropenyl-substituted alkanehydrocarbons. Such reaction is conventional for the introduction of anN-hydrocarbon-substituent on an amino-nitrogen and is accompanied by thesplitting out of HCl. For example in the reaction of ethyl chloride withethylene diamine

    C.sub.2 H.sub.5 Cl + H.sub.2 N--C.sub.2 H.sub.4 NH.sub.2 →C.sub.2 H.sub.5 --NH--C.sub.2 H.sub.4 NH.sub.2 + HCl .

As in that reaction 1 or 4 moles of ethyl chloride can react with ethylethylene diamine to form N-ethyl and N-diethyl, N,N'-diethyl,N,N,N'-triethyl and N,N'-tetraethyl ethylenediamine, one or more molesof 1-chloropropenyl- and 1-chloro-2-methylpropenyl-substituted alkanescan react with bis-(aminoalkyl) piperazine, alkylene polyamine, orN,N-di(hydroxyalkyl) alkylene polyamine to form N-mono-, di-, tri-, etc.substituted products. However, in general only one hydrogen of a primaryaminonitrogen is replaced by the rather large 1-propenyl- or1-(2-chloropropenyl)-substituted alkane.

The following illustrate the classes of the bis-(aminoalkyl) piperazine,alkylene polyamine and N,N-di(hydroxyalkyl) alkylene polyamine to beN-substituted by the 1-propenyl- or 1-(2-methylpropenyl)-substitutedalkane (hereinafter "Z") according to this invention.

Bis-(aminoalkyl) piperazine

These amines are derivatives of di-nitrogen-containing heterocyclicdiamine, piperazine, which is the cyclic diamine obtained from two moleseach of ammonia and ethylene chloride: ##EQU3## and are, therefore,N₁,N₄ -bis(aminoalkyl) piperazines having the general formula: ##EQU4##wherein m is an integer from 1 to 10 as in bis(aminomethyl)-,bis(aminoethyl)-, bis(aminopropyl)-, bis(aminobutyl)-,bis(aminopentyl)-, bis(aminohexyl)-, bis(aminoheptyl)-,bis(aminooctyl)-, bis(aminononyl)-, and bis(aminodecyl)-piperazine.

Alkylene Polyamine

These amines can be represented by the formula H₂ N--(--A--NH)_(n) Hwherein n is an integer from 1 to 10 and --A-- is a divalent hydrocarbonradical containing 1 to 10 methylene radicals. For example the alkylenepolyamines can be diaminoalkanes including methylene diamine,1,2-dimethylene diamine, 1,3-trimethylene diamine, 1,4-tetramethylenediamine, 1,5-pentamethylene diamine, 1,6-hexamethylene diamine,1,7-heptamethylene diamine, 1,8-octamethylene diamine, 1,9-nonamethylenediamine and decamethylene diamine. Said alkylene polyamines also includethe amines wherein --A-- is ethylene, propylene, butylene, pentylene,hexylene, heptylene, octylene, nonylene, and decylene radicals as areobtained by the known reaction of 1 to 10 moles of the appropriatedichloroalkane (e.g. ethylene, propylene, etc.)dichloride with 2 to 11moles of ammonia. Of these members of alkylene polyamines the ethyleneor propylene polyamines having 2 to 10 ethylene or propylene radicalsand 3 to 11 amino (2 primary amino and 1-9 secondary amino) radicals areavailable as commercial products. The most preferred of these arediethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine, hexaethyleneheptamine, dipropylenetriamine,tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine,and hexapropyleneheptamine.

Di(hydroxyalkyl) Alkylene Polyamine

These amines have two hydrogens of the same primary amino radical of thealkylene polyamines replaced by a hydroxyalkyl group, for example, bythe known reaction of two moles of an alkylene oxide (e.g. ethylene orpropylene oxide) or alkylene diol (ethylene or propylene glycol) oralkylene chlorohydrin (e.g. ethylene or propylene chlorohydrin) with thealkylene polyamine. Such di(hydroxyalkyl) alkylene polyamines have theformula (HO--X--)₂ N--(--A--NH)_(n) H wherein X is ethylene or propyleneand --A-- and n have the above meanings. Specific illustrative membersof the di(hydroxyalkyl) alkylene polyamines areN-di(hydroxyethyl)ethylene diamine, N-di(hydroxyethyl) diethylenetriamine, N-di(hydroxyethyl) triethylene tetramine N-di(hydroxyethyl)tetraethylenepentamine, N-di(hydroxyethyl) pentaethylene hexamine,N-di(hydroxypropyl) propylenediamine, N-di(hydroxypropyl)dipropylenetriamine, N-di(hydroxyethyl) tripropylenetriamine,N-di(hydroxyethyl) tetrapropylenepentamine, and N-di(hydroxypropyl)pentapropylene hexamine, that is wherein X is --C₂ H₄ --or --C₃ H₆ --.

1-Chloropropenyl or 1-Chloro-2-Methylpropenyl Alkane

These reactants are obtained by the sulfuryl chloride 1,2-dichlorinationof preferably propene or butylene polymer followed preferably by thethermal dehydrochlorination of the 1,2-dichloride product of the firststep. Said propene or butene polymer, respectively, have the singleterminal propenyl or 2-methylpropenyl group with the remainder of thepolymer entities being substantially alkane in nature because of therepeating propyl or butyl groups to provide a total of 25 to 180 numberaverage carbon atoms in the polymer entities. Such polymers havehereinbefore been identified by the formula ##EQU5## wherein R' ishydrogen in the propene polymer and methyl in the butylene polymer andwherein R contains 21 to 177 carbon atoms (7 to 59 propyl groups) in thepropene polymer or 20 to 176 carbon atoms (5 to 44 butylene) groups inthe butylene polymer.

The following two examples illustrate preparation of1-chloro-2-methylpropenyl alkane in which R contains repeating butylunits. Since the butylene polymers used have 2000 and 330 number averagemolecular weight (M_(n)) the number average carbon atoms are,respectively, 142 and 23 and the butyl groups in R are, respectively,138 and 19. Examples 1 and 2 illustrate 1,2-dichlorination of the twobutylene polymers with sulfuryl chloride followed by the preferredthermal dehydrochlorination (thermal cracking) of the 1,2-dichlorides toobtain the 1-chloro-2-methylpropenyl terminated polybutylgroups-containing alkane products.

EXAMPLE 1

A mixture of 1500 grams (0.75 mole) of a polybutene having a numberaverage molecular weight (M_(n)) of about 2000 and 1000 cc benzene arestirred at 150°F. while 150 grams (1.12 mole) SO₂ Cl₂ is added overabout one hour in a 5 liter 3 necked flask equipped with an efficientstirrer, condenser, thermometer, drying tube and dropping funnel andthen the stirred reaction mixture is heated to 175°F. and held there forabout 2 hours. The resulting reaction mixture is stirred and heated to340°F. with nitrogen injection into the liquid to remove HCl and SO₂ andbenzene solvent. Residual SO₂ and HCl are removed by holding the stirredreaction mixture at 340°F. for 60 minutes. The residual liquid isviscous liquid deep amber in color and has a M_(n) of 2015, 2.10%chlorine and 0.02% sulfur. The chlorine content is over the theoretical1.75% chlorine for the desired 1-chloro-2-methylpropenyl terminatedproduct is indicative of a product having 75% 1-chloro-2-methyl propenylterminated product and 25% original 1,2-dichloride of the butylenepolymer.

EXAMPLE 2

In the apparatus described in Example 1 there are combined five moles ofa polybutene having a M_(n) of about 330 and 1000 cc benzene. Themixture is heated to 150°F. with stirring and 750 grams SO₂ Cl₂ (5.6moles) is added over a 1 hour period. This mixture is stirred and heatedto 175°F. and held at 175°F. for 2.5 hours. Thereafter the temperatureof resulting stirred mixture is increased to 350°F., nitrogen gas isinjected into the liquid while it is being heated and the 350°F.temperature is maintained for about 1 hour to remove gaseous by-productsand benzene solvent. The SO₂ and HCl free viscous liquid is filtered.The filtered product thus prepared will be found to contain about 10%chlorine which is only 4.0% excess over the theoretical amount ofchlorine in the corresponding 1-chloro-2-methylpropenyl terminatedbutylene polymer. The dehydrochlorination step of Examples 1 and 2 canbe conducted to remove all excess chlorine by increasing the thermalcracking temperature and/or increasing the time of the inert gasinjection.

EXAMPLE 3

N-polybutenyl tetraethylene pentamine is prepared by heating the productof Example 1 (1500 grams) and 1500 cc of xylene to 285°F. and thenadding 135 grams (0.71 mole) tetraethylene pentamine dropwise over aperiod of about 2 hours. Thereafter the reaction mixture is stirred andmaintained at 285°F. for 16-18 hours. The reaction mixture is cooled, to240°F., and excess aqueous sodium hydroxide is added, with stirring, toneutralize retained HCl. Stirring is stopped, the aqueous phase ispermitted to settle. The aqueous phase contains the HCl in neutralizedform (NaCl) and excess NaOH. The clear upper xylene solution is removedby decantation, xylene is distilled therefrom assisted with nitrogen gasinjection into the liquid while distilling xylene and the distillationresidue is dissolved in 1050 grams SAE 5W oil. The solution is filteredwith a diatomaceous filter aid. In this manner a 2300 gram yield of oilsolution of N-substituted tetraethylene pentamine having a nitrogencontent of 1.0%, chlorine content of 0.45%, sulfur content of 0.11% anda viscosity at 210°F. of 840 SSU. The amine yield is about 70% based ontetraethylene pentamine charged. Said N-substitutedtetraethylenepentamine is believed to have the formula H--(NH--C₂ H₄)₄--NH--Z

wherein Z has the formula ##EQU6##

EXAMPLE 4

The 1-chloro-2-methylpropenyl terminated butylene polymer prepared asdescribed in Example 1 is dissolved in toluene and reacted withbis-(aminopropyl) piperazine in a molar ratio of 2.0 mole of saidmonochloride to 1.0 mole of bis(aminopropyl) piperazine at a temperatureof 230°F. for 16-18 hours. The stirred reaction mixture is cooled to220°F., residual HCl is taken up when neutralized with aqueous caustic,the aqueous phase permitted to settle and the organic phase recovered bydecantation. The recovered organic phase is heated to drive off toluene.The residue is dissolved in SAE 5W mineral oil to provide a 50%concentration of the N,N-disubstituted bis(aminopropyl) piperazinebelieved to have the formula ##EQU7## wherein each Z is ##EQU8##

EXAMPLE 5

The 1-chloro-2-methylpropenyl terminated butylene polymer productprepared as described in Example 1 is dissolved in xylene and is reactedwith N-di(hydroxyethyl) diethylene triamine as described in Example 3but in a 1.0:1.0 molar ratio of reactants at 250°F. for about 16 hours.Thereafter the mixture is neutralized with aqueous caustic. The xylenephase is recovered, xylene is distilled therefrom and the residuedissolved in SAE 5W oil to a product having 55% of the N'-substitutedN-di(hydroxyethyl) diethylene triamine product believed to have theformula Z--NH--C₂ H₄ --NH--C₂ H₄ --N--(C₂ H₄ OH)₂ wherein Z is thesubstituent shown in Examples 3 and 4.

EXAMPLE 6

The 1-chloro-2-methylpropenyl terminated butylene polymer product ofExample 2 (2.0 moles) is dissolved in 1250 grams xylene and is reactedwith ethylene diamine (2.2 moles) for 16 hours at 250°F. Thereafter themixture is neutralized with aqueous sodium carbonate and the xylenelayer, after settling, is recovered by decantation. The N-polybutylallylethylene diamine content of the xylene solution is determined from thenitrogen content of the solution and said amine content is adjusted to50% concentration by evaporation of all the xylene and dilution with SAE5W oil.

The N-substituted ethylene diamine of Example 6 is believed to have theformula Z--NH--C₂ H₄ NH₂ wherein Z is ##EQU9##

The following N--Z substituted N₁,N₄ bis(aminoalkyl) piperazine,di(hydroxyalkyl) alkylene polyamine and alkylene polyamine products ofthis invention can be prepared in the manner described in Examples 3-6:##EQU10##

    Z--NH--C.sub.2 H.sub.5 N--(C.sub.2 H.sub.5 OH).sub.2

    Z--NH--(CH.sub.2).sub.6 --NH--Z

    z--nh--(c.sub.2 h.sub.4 nh).sub.5 --z

wherein Z is C₃ H₇ (C₃ H₆)₄₂ --CH=CH--CH₂ from dichlorination of 764M_(n) propene polymer followed by thermal cracking thereof to obtain1-chloropropenyl polypropyl product, and reaction of 1-chloropropenylpolypropyl product with N₁,N₄ -bis(aminoethyl) piperazine (2:1 moleratio): N-di(hydroxyethyl) ethylene diamine (1:1 mole ratio):hexamethylene diamine (2:1 mole ratio, and pentaethylene hexamine (2:1mole ratio).

The N-substituted tetraethylene pentamine product of Example 3 is usedin a SAE 10W 30 weight oil formulation at 5.0 volume percentconcentration in a Ford 289 cubic inch Engine Test for evaluation as adetergent at low temperature, in a SAE 30 weight oil formulation at 5.0volume percent in a Caterpillar 1-H Engine Test for high temperaturedetergency and in a two cycle engine oil at .2 volume percent added togasoline fuel used in a two cycle engine. Total sludge and varnishratings of 43 and 35, respectively (ratings of 50 represent a cleanengine) were obtained in the Ford 289 Engine Test, a passing rating withrespect to piston lacquer and ring groove filling was achieved in theCaterpillar 1-H Engine Test and a B+ ration (A is clean engine rating)was achieved in the two cycle engine test. Those ratings comparefavorably with more coupled ashless-type detergents currently incommercial use in motor oils sold for those purposes.

The invention claimed is:
 1. An N-hydrocarbyl-substitutedbis-(aminoalkyl) piperazine product having the formula ##EQU11## whereinm is an integer from 1 to 10, Z is ##EQU12## wherein R' is hydrogen ormethyl and R consists of propyl or butyl units and the total carboncontent of Z is in the range from about 25 to about 180 carbon atoms andwherein Z₁ is hydrogen or Z.
 2. The product of claim 1 wherein R' ismethyl and R has from about 5 to about 44 butyl units.
 3. TheN,N'-disubstituted N₁, N₄ -bis(aminopropyl) piperazine of the formula##EQU13## wherein each Z is ##EQU14##